Screening cosmetic composition comprising one nanopigment of metallic oxide and one fat-soluble screening polymer

ABSTRACT

The present invention is directed to a composition for screening out ultraviolet radiation, comprising, in association, at least one nanopigment of metallic oxide and at least one UV-screening fat-soluble polymer.

This is a divisional of application Ser. No. 08/896,428 filed Jul. 17,1997, now U.S. Pat. No. 5,939,053, which in turn is a divisionalapplication of Ser. No. 08/039,324 filed Apr. 23, 1993, now U.S. Pat.No. 5,733,895 which in turn is a 371 of PCT/FR92/00821 filed Aug. 25,1992.

The subject of the present invention is a composition for screening outultraviolet radiation, comprising, in association, at least onenanopigment of metallic oxide and at least one UV-screening fat-solublepolymer.

It is known that light radiation with wavelengths of between 280 and 400nm permit the tanning of the human epidermis and that rays withwavelengths of between 280 and 320 nm, known by the name UV-B, alsocause erythemas and skin burns which can hamper the development of thetan.

However, while UV-B rays with wavelengths of between 280 and 320 nm playa preponderant part in the production of solar erythema and must bescreened out, it is nevertheless a fact that UV-A rays with wavelengthsof between 320 and 400 nm which cause tanning of the skin are alsocapable of inducing its degradation especially in the case of asensitive skin or a skin continuously exposed to solar radiation. UV-Arays cause in particular a loss of elasticity of the skin and theappearance of wrinkles which result in early ageing. They promote theonset of the erythemal reaction or amplify this reaction in certainsubjects and may even be responsible for phototoxic or photoallergicreactions.

Compounds are known which have the property of absorbing ultravioletradiation in the erythemal region while allowing the radiationresponsible for tanning to pass through and it has already been proposedto use such compounds as “sunscreen” agents in cosmetic compositionswhich promote the acquisition of skin tan while avoiding skin burns andirritations.

Synthetic or natural carbon-containing polymers and siloxane polymerscarrying an ultraviolet-absorbing group are also known which possess theadvantage of reducing or even suppressing the penetration of thescreening compound into the body.

Metallic oxides such as titanium oxide are useful because of theirultraviolet ray diffusion and reflection properties over a broad band.However, the effectiveness of the cosmetic compositions containing onlymetallic oxides, expressed by the solar protection factor which isgenerally called “protection index” or PI, is inadequate for verysensitive skins or skins continuously exposed to solar radiation,especially with respect to the UV-B protection index.

The protection index or PI may be expressed by the ratio of theirradiation time required to reach the erythematogenic threshold withthe UV-screening agent to the time required to reach the erythematogenicthreshold without a UV-screening agent.

Cosmetic compositions containing only “screening polymers” have the samedisadvantage.

In the following text, a polymer of hydrocarbon or siloxane structure,carrying at least one ultraviolet-absorbing group, will be called“screening polymer”.

Moreover, at the industrial level, it is of course advantageous to haveUV-screening agents which make it possible, at low concentrations, toobtain antisun compositions with a high protection index.

The Applicant has just discovered that by combining at least onenanopigment of metallic oxide, having a particle size less than 100 nm,with at least one fat-soluble screening polymer, in a cosmeticallyacceptable carrier, there was surprisingly obtained, for a compositioncontaining a given concentration of the nanopigment and the screeningpolymer taken together, a protection index, especially a UV-B protectionindex, substantially greater than the protection indices of compositionscontaining either a nanopigment, or a screening polymer, at the sameconcentration and in the same carrier.

The subject of the present invention is therefore a cosmetic compositionfor screening out ultraviolet radiation with wavelengths of between 280and 400 nm, which contains at least one nanopigment of metallic oxideand at least one screening polymer chosen from fat-soluble polymers witha hydrocarbon structure and polymers with a siloxane structure, in acosmetically acceptable carrier.

The subject of the present invention is also a process for protectingthe human epidermis and the hair against ultraviolet radiation withwavelengths of between 280 and 400 nm, which consists in applying to theskin an effective amount of the abovementioned screening cosmeticcomposition comprising, in association, at least one nanopigment ofmetallic oxide and at least one fat-soluble screening polymer.

The pigments of metallic oxides are chosen from titanium, zinc, cerium,zirconium or iron oxides or mixtures thereof. In the presentapplication, “nanopigments” are understood to mean pigments with a meandiameter of less than 100 nanometers, preferably of between 5 and 50nanometers. These nanopigments may be coated or uncoated.

The coated pigments are pigments which have undergone one or moresurface treatments of a chemical, electronic, mechanicochemical and/ormechanical nature with compounds, as described for example in Cosmetics& Toiletries, February 1990, Vol. 105, p. 53-64, such as amino acids,beeswax, fatty acids, fatty alcohols, anionic surfactants, lecithins,sodium, potassium, zinc, iron or aluminum salts of fatty acids, metallicalkoxides (of titanium or aluminum), polyethylene, silicones, proteins(collagen, elastin), alkanolamines, silicon oxides, metallic oxides orsodium hexametaphosphate.

The coated pigments are more particularly titanium oxides coated:

with silica, such as the product “SUNVEIL” from the company IKEDA,

with silica and iron oxide, such as the product “SUNVEIL F” from thecompany IKEDA,

with silica and alumina, such as the products “MICROTITANIUM DIOXIDE MT500 SA” and “MICROTITANIUM DIOXIDE MT 100 SA” from the company TAYCA,“TIOVEIL” from the company TIOXIDE,

with alumina, such as the products “TIPAQUE TTO-55(B)” and “TIPAQUETTO-55(A)”, from the company ISHIHARA, and “UVT 14/4” from the companyKEMIRA,

with alumina and aluminum stearate, such as the product “MICROTITANIUMDIOXIDE MT 100 T” from the company TAYCA,

with alumina and aluminum laurate, such as the product “MICROTITANIUMDIOXIDE MT 100 S” from the company TAYCA,

with iron oxide and iron stearate, such as the product “MICROTITANIUMDIOXIDE MT 100 F” from the company TAYCA,

with zinc oxide and zinc stearate such as the product “BR 351” from thecompany TAYCA,

with silica, alumina and silicone, such as the products “MICROTITANIUMDIOXIDE MT 600 SAS” and “MICROTITANIUM DIOXIDE MT 500 SAS” from thecompany TAYCA,

with silica, alumina, aluminum stearate and silicone, such as theproduct “STT-30-D-S” from the company TITAN KOGYO,

with alumina and silicone, such as the product “TIPAQUE TTO-55(S)” fromthe company ISHIHARA,

with triethanolamine, such as the product “STT-65-S” from the companyTITAN KOGYO,

with stearic acid such as the product “TIPAQUE TTO-55(C)” from thecompany ISHIHARA,

with sodium hexametaphosphate, such as the product “MICROTITANIUMDIOXIDE MT 150 W” from the company TAYCA.

There may also be mentioned the mixtures of metallic oxides, especiallyof titanium dioxide and cerium dioxide, including the equiponderalmixture of titanium dioxide and cerium dioxide, coated with silica,which is sold by the company IKEDA under the name “SUN-VEIL A” as wellas the mixture of titanium dioxide and zinc dioxide coated with alumina,silica and silicone, such as the product “M 261” sold by the companyKEMIRA, or coated with alumina, silica and glycerin, such as the product“M 211” sold by the company KEMIRA.

The uncoated titanium oxides are for example sold by the company TAYCAunder the trade names “MICROTITANIUM DIOXIDE MT 500 B” or “MICROTITANIUMDIOXIDE MT 600 B”, by the company DEGUSSA under the name “P 25”, by thecompany WACKHERR under the name “Transparent titanium oxide PW”, by thecompany MIYOSHI KASEI under the name “UFTR” and by the company TOMENunder the name “ITS”.

The uncoated zinc oxides are for example sold by the company SUMITOMOunder the name “ULTRA FINE ZINC OXIDE POWDER”, by the company PRESPERSEunder the name “FINEX 25” or by the company IKEDA under the name“MZO-25”.

The uncoated cerium oxide is sold under the name “COLLOIDAL CERIUMOXIDE” by the company RHONE POULENC.

The iron oxides are for example sold by the company HILTON DAVIS underthe names “PUROXY YELLOW HIGH TRANSPARENCY”, “PURE OXY RED HIGHTRANSPARENCY” and “PUROXY BLACK HIGH TRANSPARENCY”.

According to the invention, the coated or uncoated nanopigments oftitanium oxide are particularly preferred.

The fat-soluble hydrocarbon chain-containing screening polymers usedaccording to the invention may be:

a) polyethyleneimine, chitin or chitosan polymers with an optionallysubstituted polyethylenic structure on which are grafted ultravioletradiation-absorbing molecules via an ester, amide, ether, thioether,sulfonyl or acyl functional group,

b) polymers resulting from the homo- or copolymerization of ultravioletradiation-absorbing molecules (“screening monomers”) carrying anunsaturated group chosen from the radicals: allyl, vinyl, acrylamide,methacrylamide, vinyloxycarbonylmethyl, acrylamidoalkyl and especiallyacrylamidomethyl, methacrylamidoalkyl, acrylamido(phenyl)alkyl,methacrylamido(phenyl)alkyl, acryloyloxy, acryloyloxy-alkyl andacryloyloxypolyoxyethylene, optionally with other unsaturated monomers.

By way of ultraviolet radiation-absorbing molecules, the followingcompounds may be mentioned:

benzylidenecamphor and its derivatives substituted on the benzenenucleus,

isophthalylidenecamphor and terephthalylidenecamphor, optionallysubstituted on the benzene nucleus,

cinnamic acid, optionally substituted by one or more lower alkoxy groupsand its esters,

salicylic acid and its esters,

benzoic acid and its esters,

p-aminobenzoic acid and its derivatives which are alkylated on the aminogroup and their esters,

optionally substituted hydroxybenzophenones,

optionally substituted dibenzoylmethane,

benzotriazole and 2-arylbenzotriazoles

2-arylbenzimidazoles,

2-arylbenzofurans,

2-arylbenzoxazoles,

2-arylindoles,

mono- or diphenylcyanoacrylates,

absorbers of coumarin structure.

By way of unsaturated monomers which are copolymerizable with the“screening monomers”, there may be mentioned:

acrylic, methacrylic, itaconic and crotonic acids or their esters,acrylamide and its derivatives, methacrylamide and its derivatives,acrylonitrile, methacrylonitrile, styrene, α-methylstyrene, isoprene,butadiene, ethylene, propylene, vinyl esters, vinyl ethers, vinylchlorides and fluorides, vinylidene chloride, N-vinylpyrrolidone,N-methacryloyl-D-glucosamine and monoesters and diesters of maleic andfumaric acids.

In the present invention, “fat-soluble polymer” is understood to mean apolymer which is insoluble in water at a concentration greater than 0.1%by weight, at room temperature, and which is soluble or dispersible in acosmetic oil such as isopropyl adipate at a concentration of at least 1%by weight, at room temperature.

By way of fat-soluble hydrocarbon chain-containing screening polymerswhich can be used according to the invention, there may be mentioned byway of examples:

1) the polymers containing units of formula (I):

 in which

Z denotes:

a) —CONHCH₂X, A denoting a hydrogen atom and X denoting a UV-absorbingaromatic group, such as those described in French Patents Nos.2,597,336; 2,237,912; 2,359,857 and 2,596,400, in which X is preferablychosen from benzylidenecamphor radicals optionally substituted inpositions 3 and 4 by a C₁-C₁₂ alkoxy radical or by a methylenedioxyradical, from 2-(2′-hydroxyphenyl)benzotriazole radicals optionallysubstituted in position 5′ by a methyl or tert-octyl radical, from4-methoxy-4′-tert-butyldibenzoylmethane radical, 4-hydroxybenzophenoneradical, 2-hydroxybenzophenone radical optionally substituted by amethoxy group in position 4, from radicals derived from4-hydroxycoumarin and 7-hydroxycoumarin;

where n is 0 or 1

when n=0, A represents a hydrogen atom;

when n=1, A represents a hydrogen atom or a methyl radical,

R₁, R₂, R₃, R₄ and R₅, which are identical or different, represent ahydrogen atom, a linear or branched alkyl radical having 1 to 8 carbonatoms, an alkoxy radical having 1 to 4 carbon atoms, a dialkylaminoradical or a dialkylaminoalkyl radical of formula:

in which m is 1 to 3 and R₆ represents a methyl or ethyl radical, thesaid radicals being optionally quaternized by means of a quaternizingagent chosen from the group consisting of methyl chloride, dodecylbromide, dimethyl sulfate and chloroacetic acid;

Y being zero or being capable of denoting —CH₂—,

—C(CH₃)₂—CH₂—, these polymers being described in French Patent No.2,617,399;

2) the polymers derived from vinyl acetate containing the unit offormula (II)

in which F represents a UV-absorbing radical such as those described inFrench Patents Nos. 2,197,023 and 2,359,856;

the group

being preferably chosen from a (C₁-C₄ p-dialkyl)aminobenzoate group, acinnamate group which is optionally substituted by a methoxy, asalicylate group, a diphenylcyanoacrylate group and a flufenate or3′-trifluoromethyldiphenylamine-2-carboxylate group;

3) the copolymers of polyethyleneimine with a molecular weight ofbetween 500 and 100,000 and (C₁-C₄ para-dialkyl)aminobenzoic acidchloride, such as those described in U.S. Pat. No. 3,864,473;

4) the copolymers of monomers with ethylenic unsaturations and4-(N,N-diallylamino)benzoic acid derivatives or its esters, such asthose described in U.S. Pat. No. 3,795,733;

5) the polymerization products of the monomers of formula

 in which

R denotes —(X_(n)O or CH₂CH₂—O_(n),

X denoting a divalent alkylene, arylene or alkylarylene radical,

n=1 to 1000,

R′ denotes OH, N(R₁)₂,

R₁ denotes H, alkyl, aryl or alkylaryl,

the alkyl radicals having 1 to 20 carbon atoms,

such as those described for example in Patent WO 88/09783;

6) the polymers derived from chitin and chitosan carrying at least oneUV-absorbing group of formula:

 in which:

X and Y, independently of each other, denote hydrogen, a benzoyl radicalof formula (IV) or a cinnamoyl radical of formula (V) and Y may alsodenote acetyl:

 in which formulae:

R¹, R² and R³, which are identical or different, denote hydrogen, C₁-C₄alkoxy, hydroxy or:

 R⁴ denoting hydrogen, C₁-C₄ alkyl, C₂-C₄ monohydroxyalkyl or C₂-C₄dihydroxy alkyl, provided that at least one of the groups R¹, R² or R³does not denote hydrogen and that at most one of the groups R¹, R² or R³denotes:

R⁵ denotes C₁-C₄ alkoxy

p=3-20,000,

provided that when X denotes hydrogen, Y denotes neither hydrogen noracetyl;

such polymers are described in German Patent Application No. 3,912,122.

The preferred hydrocarbon chain-containing fat-soluble screeningpolymers according to the invention are polyacrylamides with optionallysubstituted benzylidenecamphor graft units X as defined above in 1)a).

The siloxane chain-containing screening polymers used according to theinvention are diorganopolysiloxanes containing in their molecule atleast one unit of formula:

in which

R′ denotes a saturated or unsaturated C₁-C₃₀ hydrocarbon group, ahalogenated C₁-C₈ hydrocarbon group or a trimethylsilyloxy group;

a=1 or 2;

X=—A—Y

where A represents a divalent aliphatic or aromatic hydrocarbon radicalcontaining at least 2 carbon atoms and optionally containing one or moreoxygen atoms;

Y represents the residue of an ultraviolet radiation-screening molecule.

In addition to the units of formula (VI), the diorganopolysiloxane maycontain units of formulae:

in which R′ and a have the same meaning as in formula (VI);

b is an integer denoting 1, 2 or 3;

Z=—O—Y, Y having the same meaning as in formula (VI).

By way of hydrocarbon group, there may be mentioned a C₁-C₃₀ alkylradical, a C₂-C₃₀ alkenyl radical, a cycloalkyl or aromatic radical suchas a phenyl or tolyl radical.

By way of halogenated hydrocarbon group, there may be mentioned a3,3,3-trifluoropropyl radical.

In the diorganopolysiloxane consisting of (VI), and optionally (VII) and(VIII), units, at least 40% in numerical terms of the R′ radicals aremethyl radicals. The total number of (VI), (VII) and (VIII) units ispreferably less than or equal to 250 and is in particular between 2 and50.

Y preferably represents:

a benzylidenecamphor residue which is optionally substituted on thebenzene nucleus by hydroxyl, alkyl or C₁-C₅ alkoxy radicals;

a C₁-C₈ dialkyl benzalmalonate residue which is optionally substitutedon the benzene nucleus by hydroxy, alkyl or C₁-C₆ alkoxy radicals;

a 2-(2′-hydroxyphenyl)benzotriazole residue optionally carrying on oneof the aromatic nuclei C₁-C₈ alkyl or C₂-C₈ alkenyl, halogen, alkoxy,carboxy, hydroxy, amino or tetraalkylpiperidyl substituents;

a dibenzoylmethane residue optionally carrying C₁-C₈ alkyl or alkoxy orhydroxy substituents;

a benzophenone residue optionally carrying C₁-C₈ alkyl or alkoxy orhydroxy substituents;

a benzoate residue substituted by hydroxy, C₁-C₆ alkoxy, amino or mono-or di-(C₁-C₅ alkyl)amino radicals.

Such siloxane chain-containing screening polymers are described inEuropean Patent Applications Nos. 0,335,777; 0,392,882; 0,388,218;0,392,883; 0,383,655 and 0,389,337 and in French Patents 2,550,787 and2,657,351 and in U.S. Pat. Nos. 4,696,969; 4,554,369; 4,562,278;3,513,184 and 4,859,759.

The screening silicones preferred for use according to the invention arethose in which the radical Y denotes a benzylidenecamphor radical or anoptionally substituted 2-(2′-hydroxyphenyl)benzotriazole radical asdefined above.

The concentration of nanopigments in the compositions according to theinvention is between 0.1 and 15% by weight and preferably between 0.5and 10% by weight relative to the total weight of the composition.

The screening polymer(s) are present at a total concentration of between0.1 and 15% by weight and preferably between 0.5 and 10% by weightrelative to the total weight of the composition.

The nanopigment(s)/screening polymer(s) ratio by weight isadvantageously between 0.1 and 10 and preferably between 0.5 and 5.

The cosmetic composition of the invention may be used as composition forprotecting the human epidermis or the hair against ultraviolet rays, asan anti-sun composition or as a make-up product.

This composition may be provided in particular in the form of a lotion,a thickened lotion, a gel, an oil, a vesicular dispersion, a cream, amilk, a powder or a solid stick and may optionally be packaged as anaerosol and provided in the form of a foam or a spray.

It may contain the cosmetic adjuvants generally used, such as fattysubstances, organic solvents, silicones, thickeners, emollients, UV-A,UV-B or broad band sunscreen agents, antifoaming agents, moisturizingagents, perfumes, preservatives, surfactants, fillers, sequestrants,anionic, cationic, nonionic and amphoteric polymers or mixtures thereof,propellants, alkalinizing or acidifying agents, colorants, pigments ofmetallic oxides with a particle size of between 100 nm and 20,000 nmsuch as iron oxides, or any other ingredient generally used in thecosmetic field.

The fatty substances may consist of an oil or a wax or a mixturethereof, fatty acids, fatty alcohols, vaseline, paraffin, lanolin,hydrogenated lanolin or acetylated lanolin.

The oils are chosen from animal, vegetable, mineral or synthetic oilsand especially hydrogenated palm oil, hydrogenated castor oil, vaselineoil, paraffin oil, Purcellin oil, silicone oils and isoparaffins.

The waxes are chosen from animal, fossile, vegetable, mineral orsynthetic waxes. There may be mentioned especially beeswaxes, Carnaubawax, Candelilla wax, sugar cane wax, Japan wax, ozokerites, Montan wax,microcrystalline waxes, paraffins, silicone waxes and resins.

When the cosmetic composition according to the invention is used forprotecting the human epidermis against UV rays, or as an anti-suncomposition, it may be provided in the form of a suspension or adispersion in solvents or fatty substances, or alternatively in the formof an emulsion such as a cream or a milk, in the form of an ointment, agel, a solid stick or an aerosol foam.

The emulsions may contain, in addition, anionic, nonionic, cationic oramphoteric surface-active agents.

It may also be provided in the form of a vesicular dispersion of ionicor nonionic amphiphilic lipids which is prepared according to knownprocesses. The lipids may for example be swollen in an aqueous solutionto form spherules dispersed in the aqueous medium as described in thepublication BANGRAM, STANDISH & WATKINS, J. Mol. Biol., 13, 238 (1965)or in Patents FR-2,315,991 and 2,416,008 by the Applicant.

When the cosmetic composition according to the invention is used forprotecting the hair, it may be provided in the form of a rinse-offshampoo, lotion, gel or composition to be applied before or aftershampooing, before or after dyeing or bleaching, before, during or afterpermenent waving or hair straightening, a hair styling or treatmentlotion or gel, a lotion or gel for blow drying or hair setting, a hairlacquer, a composition for permanent waving or hair straightening, andfor dyeing or bleaching the hair.

When the composition is used as a make-up product for the eyelashes,eyebrows or the skin, such as a cream for treating the epidermis, afoundation, a lipstick, an eyeshadow, a blusher, a mascara or an eyeliner, it may be provided in solid or pasty, anhydrous or aqueous form,such as oil-in-water or water-in-oil emulsions, vesicular dispersions oralternatively suspensions.

The subject of the invention is also a process for protecting the humanepidermis and the hair against ultraviolet radiation, consisting inapplying to the skin or the hair an effective quantity of the abovecosmetic composition.

The invention will be illustrated more clearly by the nonlimitingexamples below.

EXAMPLE 1

An anti-sun cream of the following composition is prepared:

Titanium oxide coated with iron oxide and iron stearate 5 g (meandiameter 15 nm) sold under the name “MICROTITANIUM DIOXIDE MT 100 F” bythe company TAYCA Polydimethylsiloxane containing a2-(3′-trimethylene-5′- 5 g methyl-2′-hydroxyphenyl)benzotriazole graftunit of formula:

according to Example 1 of Application EP 0,388,218 Mixture of glycerolstearate and polyethylene glycol 1 g stearate containing 100 moles ofethylene oxide sold under the name “ARLACEL 165” by the company ICIIsostearic acid 2 g 2-Octyldodecanol 15 g Stearyl alcohol 1 g Glycerin 3g Sorbitol in aqueous solution at 70% AI 1.4 g AI Cross-linkedpolyacrylic acid sold under the name 0.3 g “CARBOPOL 940” by the companyGOODRICH Triethanolamine 0.4 g Preservatives, antioxidant qs Perfume qsWater qs 100 g

EXAMPLE 2

An anti-sun cream of the following composition is prepared:

Titanium oxide coated with iron oxide and iron stearate 5 g (meandiameter 15 nm) sold under the name “MICROTITANIUM DIOXIDE MT 100 F” bythe company TAYCA Poly(4′-acrylamidomethyl-3-benzylidenecamphor) of 5 gExample 1 of French Patent No. 2,597,336 consisting of the units:

Mixture of glycerol stearate and polyethylene glycol 1 g stearatecontaining 100 moles of ethylene oxide sold under the name “ARLACEL 165”by the company ICI Isostearic acid 2 g 2-Octyldodecanol 15 g Stearylalcohol 1 g Glycerin 3 g Sorbitol in aqueous solution at 70% AI 1.4 g AICross-linked polyacrylic acid sold under the name 0.3 g “CARBOPOL 940”by the company GOODRICH Triethanolamine 0.4 g Preservatives, antioxidantqs Perfume qs Water qs 100 g

EXAMPLE 3

An anti-sun O/W emulsion of the following composition is prepared:

Mixture of glycerol stearate and polyethylene glycol stearate containing100 moles of 2 g ethylene oxide sold under the name “ARLACEL 165” by thecompany ICI Vaseline oil 8 g Stearic acid 2 g Lanolin 2 g Stearylalcohol 1 g Polydimethylsiloxanecontaining2-(3′-trimethylene-2′-hydroxy-5′- 2 gmethylphenyl)-benzotriazole graft units according to Application EP0,392,883

Glycerin 3 g Sorbitol in aqueous solution at 70% AI 1.4 g AIHydroxyethyl cellulose modified by a cetyl chain sold under the name 0.5g “NATROSOL PLUS GRADE 330 CS” by the company AQUALON Potassiumhexadecylphosphate 0.5 g Sodium acetate monohydrate 0.2 g Colloidalcerium oxide sold in aqueous solution at 20% AI by the company 2 g AIRHONE POULENC under the name “COLLOIDAL CERIUM OXIDE” Preservatives qsWater qs 100 g

EXAMPLE 4

An anti-sun O/W emulsion of the following composition is prepared:

Mixture of glycerol stearate and polyethylene glycol 2 g stearatecontaining 100 moles of ethylene oxide sold under the name “ARLACEL 165”by the company ICI Vaseline oil 8 g Stearic acid 2 g Lanolin 2 g Stearylalcohol 1 g Mixture of polydimethylsiloxanes containing 4′-tri-methyl- 2g eneoxy-3-benzylidenecamphor and 4′-oxy-3-benzylidene- camphor graftunits, which is prepared according to Application EP 0,335,777, andhaving the formula:

consisting of about: 55% polydimethylsiloxane in which x = 0 to 20, y =1 to 4, z = 0 5% polydimethylsiloxane in which x = 0 to 21, y = 0, z = 1to 4 40% polydimethylsiloxane in which x = 0 to 16, y = 1 to 3, z = 1 to3, BC denoting the 3-benzylidenecamphor radical Glycerin 3 g Sorbitol inaqueous solution at 70% AI 1.4 g AI Hydroxyethyl cellulose modified by acetyl chain sold 0.5 g under the name “NATROSOL PLUS GRADE 330 CS” bythe company AQUALON Potassium hexadecylphosphate 0.5 g Sodium acetatemonohydrate 0.2 g Titanium oxide coated with iron oxide and ironstearate 2.5 g (mean diameter 15 nm) sold under the name “MICROTITANIUMDIOXIDE MT 100 F” by the company TAYCA Preservatives qs Water qs 100 g

EXAMPLE 5

An anti-sun O/W emulsion of the following composition is prepared:

Mixture of glycerol stearate and polyethylene glycole 2 g stearatecontaining 100 moles of ethylene oxide sold under the name “ARLACEL 165”by the company ICI Vaseline oil 8 g Stearic acid 2 g Lanolin 2 g Stearylalcohol 1 g Graft polydimethylsiloxane derived from benzophenone 2 g offormula:

Glycerin 3 g Sorbitol in aqueous solution at 70% AI 1.4 g AIHydroxyethyl cellulose modified by a cetyl chain 0.5 g sold under thename “NATROSOL PLUS GRADE 330 CS” by the company AQUALON Potassiumhexadecylphosphate 0.5 g Sodium acetate monohydrate 0.2 g Zinc oxidesold under the name “ULTRA FINE ZINC 2 g OXIDE POWDER” by the companySUMITOMO Preservatives qs Water qs 100 g

EXAMPLE 6

A cream gel of the following composition is prepared:

Glycerin 3 g Vaseline oil 5 g Oil-in-water emulsion of cross-linkedacrylamide/sodium 2-acrylamido-2- 1.2 g AI methylpropanesulfonatecopolymer, sold by the company SEPPIC in copolymer under the name“SEPIGEL 305” with 40% AI in copolymer Titanium oxide coated with ironoxide and iron stearate (mean diameter 15 nm) sold 1.33 g under the name“MICROTITANIUM DIOXIDE MT 100 F” by the company TAYCA Graftpolydimethylsiloxane derived from benzophenone of formula: 2.67 g

according to French Patent Application FR 2,657,351 Mixture ofdimethiconol (13%), octamethylcyclotetrasiloxane and decamethyl- 5 gcyclopentasiloxane (87%), sold under the name “Q2-1401” by the companyDOW CORNING Methyl polymethacrylate powder (15μ) sold under the name 3 g“MICROPEARL M 100” by the company SEPPIC Preservatives qs Water qs 100 g

What is claimed is:
 1. Screening cosmetic composition comprising, in acomsmetically acceptable carrier, at least one nanopigment of metallicoxides selected from the group consisting of titanium, zinc, cerium,zirconium and iron oxides and mixtures thereof, with a mean diameter ofless than 100 nm, and at least one polymer carrying at least oneultraviolet-absorbing group which is a fat-soluble polymer with asiloxane structure, said polymer with siloxane structure consisting of adiorganopolysiloxane containing in its molecule at least one unit offormula:

in which R′ denotes a saturated or unsaturated C₁-C₃₀ hydrocarbon group,a halogenated C₁-C₈ hydrocarbon group or a trimethylsilyloxy group; a=1or 2; X=—A—Y where A represents a divalent aliphatic or aromatichydrocarbon radical containing at least 2 carbon atoms and optionallycontaining one or more oxygen atoms, and Y represents the residue of anultraviolet radiation-screening molecule, which is a2-(2′-hydroxyphenyl)benzotriazole residue which is unsubstituted orcarrying on one of the aromatic nuclei C₁-C₈ alkyl, C₂-C₈ alkenyl,halogen, alkoxy, carboxy, hydroxy or amino substituents.
 2. Cosmeticcomposition according to claim 1, wherein the nanopigments of metallicoxides have a diameter of between 5 and 50 nm.
 3. Cosmetic compositionaccording to claim 1, wherein the metallic oxide is titanium oxide. 4.Cosmetic composition according to claim 1, wherein the nanopigment ofmetallic oxides is a coated pigment having undergone one or more surfacetreatments of a chemical, electronic, mechanicochemical or mechanicalnature with compounds chosen from amino acids, beeswax, fatty acids,fatty alcohols, anionic surfactants, lecithins, sodium, potassium, zinc,iron or aluminum salts of fatty acids, metallic alkoxides, polyethylene,silicones, proteins, alkanolamines, silicon oxides, metallic oxides andsodium hexametaphosphate.
 5. Cosmetic composition according to claim 4,wherein the coated nanopigment of metallic oxides is a pigment oftitanium oxide coated with silica, with silica and alumina, with silicaand iron oxide, with alumina and silicone, with alumina, with aluminaand aluminum stearate, with alumina and aluminum laurate, with ironoxide and iron stearate, with zinc oxide and zinc stearate, with silicaand alumina and silicone, with silica and alumina and aluminum stearateand silicone, with triethanolamine, with stearic acid or with sodiumhexametaphosphate.
 6. Cosmetic composition according to claim 1, whichcontains 0.1 to 15% by weight, relative to the total weight of thecomposition, of at least one nanopigment of metallic oxides.
 7. Cosmeticcomposition according to claim 1, wherein the diorganopolysiloxanecontains, in addition, units having the formulae:

in which R′ and a have the meanings indicated in claim 6, b is aninteger equal to 1, 2 or 3, Z=—O—Y, Y having the same meaning as inclaim 6, at least 40% in numerical terms of the R′ radicals denotingmethyl.
 8. Cosmetic composition according to claim 1, which comprises apolydimethylsiloxane with2-(3′-trimethylene-5′-methyl-2′-hydroxyphenyl)benzotriazole graftunit(s).
 9. Cosmetic composition according to claim 1, which contains0.1 to 15% by weight, relative to the total weight of the composition,of at least one fat-soluble screening polymer with siloxane structure.10. Cosmetic composition according to claim 1, wherein thenanopigment(s)/screening polymer(s) ratio by weight is between 0.1 and10 and preferably between 0.5 and
 5. 11. Cosmetic composition accordingto claim 1, which is a composition for protecting the human epidermis oran anti-sun composition and is in the form of a lotion, a thickenedlotion, a gel, an oil, a vesicular dispersion, a cream, a milk, apowder, a solid stick, a foam or a spray.
 12. Process for protecting thehuman epidermis and the hair against ultraviolet radiation ofwavelengths of between 280 and 400 nm, which consists in applying to theskin or the hair an effective quantity of a cosmetic compositionaccording to claim
 1. 13. Cosmetic composition according to claim 1,which is a make-up composition for the eyelashes, eyebrows or skin andis in solid or pasty, anhydrous or aqueous form, as emulsion, suspensionor vesicular dispersion.
 14. Cosmetic composition according to claim 1,which is used for protecting the hair against ultraviolet rays and is inthe form of a rinse-off shampoo, lotion, gel or composition to beapplied before or after shampooing, before or after dyeing or bleaching,before, during or after permanent waving or hair straightening, a hairstyling or treatment lotion or gel, a lotion or gel for blow drying orhair setting, a hair lacquer, a composition for permanent waving or hairstraightening, and for dyeing or bleaching the hair.
 15. Cosmeticcomposition according to claim 11, which comprises, in addition,cosmetic adjuvants selected from the group consisting of fattysubstances, organic solvents, silicones, thickeners, emollients, UV-A,UV-B or broad band sunscreen agents, antifoaming agents, moisturizingagents, perfumes, preservatives, surfactants, fillers, sequestrants,anionic, cationic, nonionic and amphoteric polymers or mixtures thereof,propellants, alkalinizing or acidifying agents, colorants and pigmentsof metallic oxides with a particle size of between 100 nm and 20,000 nm.